CN114466950A - Sliding member, method for producing same, and coating film - Google Patents

Sliding member, method for producing same, and coating film Download PDF

Info

Publication number
CN114466950A
CN114466950A CN202080068880.XA CN202080068880A CN114466950A CN 114466950 A CN114466950 A CN 114466950A CN 202080068880 A CN202080068880 A CN 202080068880A CN 114466950 A CN114466950 A CN 114466950A
Authority
CN
China
Prior art keywords
hard carbon
carbon layer
black
white
coating film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202080068880.XA
Other languages
Chinese (zh)
Inventor
冈崎孝弘
杉浦宏幸
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Piston Ring Co Ltd
Original Assignee
Nippon Piston Ring Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Piston Ring Co Ltd filed Critical Nippon Piston Ring Co Ltd
Publication of CN114466950A publication Critical patent/CN114466950A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
    • C10M103/02—Carbon; Graphite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/028—Physical treatment to alter the texture of the substrate surface, e.g. grinding, polishing
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0605—Carbon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3435—Applying energy to the substrate during sputtering
    • C23C14/345—Applying energy to the substrate during sputtering using substrate bias
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/54—Controlling or regulating the coating process
    • C23C14/541—Heating or cooling of the substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/044—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material coatings specially adapted for cutting tools or wear applications
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/046—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material with at least one amorphous inorganic material layer, e.g. DLC, a-C:H, a-C:Me, the layer being doped or not
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
    • C23C28/42—Coatings including alternating layers following a pattern, a periodic or defined repetition characterized by the composition of the alternating layers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
    • C23C28/44—Coatings including alternating layers following a pattern, a periodic or defined repetition characterized by a measurable physical property of the alternating layer or system, e.g. thickness, density, hardness
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J9/00—Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction
    • F16J9/12—Details
    • F16J9/20—Rings with special cross-section; Oil-scraping rings
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J9/00—Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction
    • F16J9/26—Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction characterised by the use of particular materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/04—Elements
    • C10M2201/041—Carbon; Graphite; Carbon black
    • C10M2201/0413—Carbon; Graphite; Carbon black used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/023—Multi-layer lubricant coatings

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • General Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physical Vapour Deposition (AREA)
  • Pistons, Piston Rings, And Cylinders (AREA)

Abstract

The present invention addresses the problem of providing a sliding member having a coating film that exhibits constant and stable chipping resistance and wear resistance and that has excellent peeling resistance (adhesion), and also providing such a coating film. The sliding member (10) has a coating film (1) on a sliding surface (16) on a base material (11), and when a cross section of the coating film (1) is observed by a bright field TEM image, the sliding member is wrappedRepeating units comprising a black hard carbon layer (B) relatively represented by black and a white hard carbon layer (W) relatively represented by white are laminated in the thickness direction (Y) and have a total thickness in the range of 1 to 50 [ mu ] m, and in the adjacent black hard carbon layer (B) and white hard carbon layer (W), the hardness of the white hard carbon layer (W) is higher than that of the black hard carbon layer (B), and [ sp ] of the white hard carbon layer (W)2/(sp2+sp3)]Is larger than the black hard carbon layer (B).

Description

Sliding member, method for producing same, and coating film
Technical Field
The invention relates to a sliding member, a method of manufacturing the same, and a coating film. More specifically, the present invention relates to a sliding member having excellent peeling resistance (adhesion) while exhibiting constant and stable chipping resistance and abrasion resistance, a method for producing the same, and a coating film.
Background
In recent years, in various industrial fields, particularly in the automotive field, studies have been extensively conducted on hard carbon layers as coating films for the surfaces of sliding members requiring slidability, such as engine substrates and other machine substrates. The hard carbon layer is generally referred to by various names such as a diamond-like carbon (DLC) layer, an amorphous carbon layer, an i-carbon layer, and a diamond-like carbon layer. Such a hard carbon layer is structurally classified as amorphous.
It is considered that a single bond as seen in diamond crystals and a double bond as seen in graphite crystals are mixedly present in the hard carbon layer. The hard carbon layer has high hardness and high wear resistance, excellent chemical stability, and the like, as diamond crystals, and also has low hardness, high lubricity, excellent target adaptability, and the like, as graphite crystals. Further, since the hard carbon layer is amorphous, it is excellent in flatness, and also has low friction (i.e., a small friction coefficient) when it is in direct contact with a target material and excellent target adaptability.
Chipping resistance (chipping resistance) and wear resistance are important characteristics for a sliding surface of a sliding member. However, since the chipping resistance (chipping resistance) and the wear resistance are in a trade-off relationship, it is difficult to provide a coating film satisfying these characteristics. As a means for solving the problem, it has been studied to provide a hard carbon layer having a low hardness or a layer in which a hard carbon having a low hardness and a hard carbon having a high hardness are mixed, thereby achieving both chipping resistance and wear resistance.
However, it is still insufficient to achieve both chipping resistance and wear resistance. In addition to chipping resistance and wear resistance, low friction properties and peeling resistance are required for a coating film provided on a sliding member to which a high load is applied, such as a piston ring, but improvement of these properties is not sufficient. In response to such a problem, various techniques have been proposed in recent years.
For example, patent document 1 proposes a technique of forming a thick hard carbon layer having excellent durability by a PVD method, and improving low friction property and peeling resistance while satisfying both chipping resistance and wear resistance of the formed hard carbon layer. This technique relates to a coating film that coats a surface of a substrate, wherein a white hard carbon layer represented by white and a black hard carbon layer represented by black are alternately laminated in a thickness direction and have a total film thickness of more than 1 μm and 50 μm or less, respectively, when a cross section is observed by a bright field TEM image, and the white hard carbon layer has a region that grows in a fan shape in the thickness direction.
Patent document 2 proposes a sliding member having a coating film exhibiting constant and stable chipping resistance and wear resistance and excellent peeling resistance (adhesion), and the coating film. The technology relates to a sliding member having a coating film formed of a hard carbon layer on a sliding surface, when a cross section of the coating film is observed by a bright field TEM image, repeating units including a black hard carbon layer represented by black and a white hard carbon layer represented by white are laminated in the thickness direction, and has a thickness in the range of 1 μm to 50 μm, the coating film having an inclined region provided on the substrate side and a homogeneous region provided on the surface side, in the inclined region, the thickness of the white hard carbon layer in the repeating unit gradually increases in the thickness direction, in the homogeneous region, the thicknesses of the white hard carbon layers in the repeating units are the same or substantially the same in the thickness direction, the inclined region has a V-shaped or radially-grown form in the thickness direction, and the homogeneous region has no V-shaped or radially-grown form in the thickness direction.
Documents of the prior art
Patent document
Patent document 1: WO2017/104822A1
Patent document 2: WO2018/235750A1
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide a novel sliding member that exhibits constant and stable chipping resistance and wear resistance, and that has excellent peel resistance (adhesion), a method for producing the sliding member, and a coating film.
Means for solving the problems
(1) A sliding member of the present invention has a coating film on a sliding surface on a base material, wherein repeating units including a black hard carbon layer represented by black and a white hard carbon layer represented by white are laminated in a thickness direction when a cross section of the coating film is observed by a bright-field TEM image, and the repeating units have a total thickness in a range of 1 [ mu ] m to 50 [ mu ] m, and in the adjacent black hard carbon layer and the white hard carbon layer, the hardness of the white hard carbon layer is higher than that of the black hard carbon layer, and the [ sp ] of the white hard carbon layer is higher than that of the black hard carbon layer2/(sp2+sp3)]Is larger than the black hard carbon layer.
As in the prior art, the relatively black hard carbon layer has a high density of [ sp ]2/(sp2+sp3)]Small ratio and excellent strength. The relatively white hard carbon layer has low density and sp2/(sp2+sp3)]Large ratio, low friction and excellent chipping resistance. However, in the present invention, in comparison with the prior art, in the adjacent black hard carbon layer and white hard carbon layer, the hardness of the white hard carbon layer is higher than that of the black hard carbon layer, and the [ sp ] of the white hard carbon layer2/(sp2+sp3)]Is larger than the black hard carbon layer. By providing a coating film as a laminate of these hard carbon layers on the sliding surface, a sliding member having excellent chipping resistance, wear resistance, and peeling resistance (adhesion) can be produced based on the lamination effect of the hard carbon layers having different properties.
In the sliding member of the present invention, the ratio of the thickness T1 of the black hard carbon layer to the thickness T2 of the white hard carbon layer (T1/T2) is in the range of 1/10 to 1.5/1. According to the present invention, the thickness ratio of the repeating units (T1/T2) can be arbitrarily controlled to be constant or variable in the thickness direction of the cover film.
In the sliding member of the present invention, the thickness of the repeating unit is in the range of 0.2 to 2 μm. According to the present invention, the thickness of each repeating unit can be arbitrarily controlled to fall within the above range.
In the sliding member of the present invention, the vickers hardness of the black hard carbon layer is in the range of 700 to 1600HV, and the vickers hardness of the white hard carbon layer is higher than the vickers hardness of the adjacent black hard carbon layer and is in the range of 1200 to 2200 HV.
In the sliding member of the present invention, the "sp" of the black hard carbon layer2/(sp2+sp3)]The ratio of [ sp ] of the white hard carbon layer is in the range of 0.05-0.752/(sp2+sp3)]Ratio of sp to the above-mentioned black hard carbon layer2/(sp2+sp3)]The ratio is large and is in the range of 0.20 to 0.80.
In the sliding member of the present invention, when a cross section is observed by a bright field TEM image, a hard carbon base film may be provided between the base material or a base film provided on the base material and the coating film.
In the sliding member according to the present invention, a hard carbon surface film may be provided on the coating film when a cross section is observed by a bright field TEM image.
In the sliding member of the present invention, the "sp" of the black hard carbon layer2/(sp2+sp3)]The ratio gradually increases from the base material side to the surface position in the thickness direction of the coating film.
In the sliding member of the present invention, the white hard carbon layer has a fine streak shape.
In the sliding member of the present invention, the black hard carbon layer has a fine streak shape.
In the sliding member according to the present invention, the black hard carbon layer and the white hard carbon layer each have a carbon layer formed by bombardment treatment directly below the black hard carbon layer and the white hard carbon layer.
In the sliding member according to the present invention, the sliding member is a piston ring.
(2) The method for producing a sliding member of the present invention includes a coating film on a sliding surface on a base material, wherein repeating units including a black hard carbon layer represented by black and a white hard carbon layer represented by white are stacked in a thickness direction when a cross section of the coating film is observed by a bright-field TEM image, and the repeating units have a total thickness in a range of 1 μm to 50 μm, the black hard carbon layer is formed under a bias that causes a temperature increase, and the white hard carbon layer is formed under a bias that does not cause a temperature increase.
(3) The coating film of the present invention is characterized in that, when a cross section is observed by a bright field TEM image, repeating units including a black hard carbon layer relatively represented by black and a white hard carbon layer relatively represented by white are laminated in a thickness direction, and have a total thickness in a range of 1 μm to 50 μm, and in the adjacent black hard carbon layer and white hard carbon layer, the hardness of the white hard carbon layer is higher than that of the black hard carbon layer, and the [ sp ] of the white hard carbon layer2/(sp2+sp3)]Is larger than the black hard carbon layer.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a novel sliding member having a coating film exhibiting constant and stable chipping resistance and wear resistance and excellent peeling resistance (adhesion), a method for producing the same, and a coating film can be provided as a sliding member and a coating film to which a high load is applied, particularly a piston ring or the like.
Drawings
Fig. 1 is a schematic cross-sectional view showing an example of a coating film provided on a sliding member of the present invention.
Fig. 2 is an explanatory view of the coating film, (a) is an example of stacking repeating units in which a black hard carbon layer B is formed and a white hard carbon layer W is formed thereon, and (B) is an example of repeating units in which a white hard carbon layer W is formed and a black hard carbon layer B is formed thereon.
Fig. 3 is a bright field TEM image showing a cross section of an example of the clad film.
Fig. 4 is a bright field TEM image showing a cross section of another example of the clad film.
Fig. 5 is a schematic cross-sectional view showing an example of a piston ring having a coating film.
Fig. 6 is a schematic diagram of a friction wear test method using an SRV tester.
Fig. 7 is a bright field TEM image showing a cross section of another example of the clad film.
Description of the symbols
1 coating film
11 base material (piston ring base material)
11a base layer
12 intermediate layer
16 sliding surface
20 frictional wear test specimen
21 sliding object
120 SRV testing machine
B black hard carbon layer
W white hard carbon layer
Y thickness direction
Detailed Description
The sliding member, the method for manufacturing the same, and the coating film according to the present invention will be described in detail with reference to the accompanying drawings. The present invention is not limited to the following description and drawings, and includes modifications within the spirit and scope thereof.
[ sliding Member ]
For example, as shown in an example of a piston ring in fig. 5, a sliding member 10 of the present invention has a coating film 1 on a sliding surface 16. When a cross section of the cover film 1 is observed by a bright field TEM image, repeating units (denoted by symbol h in fig. 2) including a black hard carbon layer B represented by black and a white hard carbon layer W represented by white are laminated in the thickness direction Y, and have a total thickness in the range of 1 μm to 50 μm. Further, the following features are provided: the hardness of the white hard carbon layer W is higher than that of the black hard carbon layer B in the adjacent black hard carbon layer B and white hard carbon layer WOf layer W [ sp2/(sp2+sp3)]Is larger than the black hard carbon layer B. In the following, in some cases, [ sp ] will be described2/(sp2+sp3)]Is simplified and expressed as "sp2/sp3Ratio ".
In the coating film 1 constituting the sliding member 10, the hard carbon layer B having a relatively black color is sp-dense and high density as in the conventional art2/sp3Small ratio, excellent strength, low density and sp of hard carbon layer with relative white color2/sp3Large ratio, low friction and excellent chipping resistance. However, unlike the conventional art, in the coating film 1, the hardness of the white hard carbon layer W is higher than that of the black hard carbon layer B, and the sp of the white hard carbon layer W is higher than that of the black hard carbon layer B, in the adjacent black hard carbon layer B and white hard carbon layer W2/sp3Is larger than the black hard carbon layer B. By providing the coating film 1 as a laminate of these hard carbon layers B, W on the sliding surface 16, a sliding member 10 excellent in chipping resistance, wear resistance, and peeling resistance (adhesion) can be produced based on the lamination effect of the hard carbon layers having different properties.
The bright field TEM image can be obtained by observing the coating film 1 formed into a thin film by using fib (focused Ion beam) at an acceleration voltage of 300kV by TEM (Transmission Electron Microscope). The thickness direction Y is a direction in which the coating films 1 are sequentially stacked on the substrate 11.
Hereinafter, the components of the sliding member will be described in detail. In the following description, a piston ring is given as an example of a sliding member in many cases, but the sliding member of the present invention is not limited to the piston ring.
(substrate)
As shown in fig. 1 and 2, the substrate 11 is a target member on which the coating film 1 is provided. The substrate 11 is not particularly limited, and examples thereof include iron-based metals, nonferrous metals, ceramics, and hard composite materials. Examples thereof include: carbon steel, alloy steel, hardened steel, high speed tool steel, cast iron, aluminum alloy, magnesium alloy, super hard alloy, and the like. Considering the film formation temperature of the coating film 1, a substrate whose characteristics do not significantly deteriorate at a temperature exceeding 200 ℃ is preferable.
The piston ring base material 11 in the case of applying the coating film 1 to the piston ring 10 includes various materials that can be used as a base material of the piston ring 10, and is not particularly limited. For example, various steel materials, stainless steel materials, casting materials, cast steel materials, and the like can be applied. Among these, martensitic stainless steel, chromium manganese steel (SUP9 material), chromium vanadium steel (SUP10 material), silicon chromium steel (SWOSC-V material), and the like are exemplified. The substrate 11 may have a base layer 11a shown in fig. 1 as needed. The base layer 11a is not particularly limited, and may be made of a material that improves adhesion to the intermediate layer 12, which will be described later.
The piston ring base material 11 may be provided with at least 1 nitride, carbonitride, carbide, or the like layer of Cr, Ti, Si, Al, or the like as the underlying layer 11 a. Examples of such a compound layer include CrN, TiN, CrAlN, TiC, TiCN, TiAlSiN, and the like. Among these, a nitride layer (not shown), a Cr-N type, Cr-B-N type, Ti-N type or other wear-resistant coating (not shown) formed by nitriding treatment is preferable. Among them, it is preferable to form a wear-resistant coating such as Cr-N type, Cr-B-N type, Ti-N type, etc. Since the piston ring 10 exhibits excellent wear resistance without providing such nitriding treatment or Cr-based or Ti-based wear-resistant coating, the nitriding treatment or the formation of Cr-based or Ti-based wear-resistant coating is not an essential configuration.
The piston ring base material 11 may be pretreated as necessary. As the pretreatment, surface polishing is preferably performed to adjust the surface roughness. The adjustment of the surface roughness is preferably performed by, for example, a method of polishing the surface of the piston ring base material 11 with a diamond abrasive to perform surface grinding. Such a piston ring base material 11 can be preferably applied as a pretreatment before forming an intermediate layer 12 or the like described later, or a pretreatment before forming a base layer 11a or the like provided in advance before forming the intermediate layer 12 or the like.
(intermediate layer)
As shown in fig. 1 and 2, an intermediate layer 12 is preferably provided between the base material 11 and the cover film 1 as needed. The intermediate layer 12 can further improve the adhesion between the base 11 and the coating film 1.
The intermediate layer 12 may be a layer containing at least 1 or 2 or more of elements such as Cr, Ti, Si, W, and B. The underlayer 11a formed of a compound such as a nitride, carbonitride, carbide, or the like containing at least 1 or 2 or more elements of Cr, Ti, Si, Al, or the like may be provided in the lower layer of the intermediate layer 12 (between the base material 11 and the intermediate layer 12). Examples of such compounds include: CrN, TiN, CrAlN, TiC, TiCN, TiAlSiN and the like. The formation of the base layer 11a provided with the intermediate layer 12 as necessary can be performed as follows: for example, the substrate 11 is placed in a chamber, vacuum is formed in the chamber, then preheating, ion cleaning, and the like are performed, and inert gas, nitrogen gas, and the like are introduced, and the process is performed by a method such as a vacuum deposition method or an ion plating method.
The intermediate layer 12 in the case of applying the coating film 1 to the piston ring 10 includes a titanium film, a chromium film, and the like. The intermediate layer 12 in this case is not necessarily provided, and the formation thereof is arbitrary. The intermediate layer 12 such as a titanium film or a chromium film can be formed by various film forming methods such as a vacuum deposition method, a sputtering method, and an ion plating method. For example, the piston ring base material 11 may be installed in a chamber, and after the chamber is evacuated, the chamber may be preheated, ion-cleaned, or the like, and an inert gas may be introduced. The thickness of the intermediate layer 12 is not particularly limited, but is preferably in the range of 0.05 μm to 2 μm. The intermediate layer 12 is preferably formed at least on an outer peripheral sliding surface 16 on which the piston ring 10 slides in contact with a cylinder liner (not shown), but may be formed on other surfaces, for example, an upper surface, a lower surface, and an inner peripheral surface of the piston ring 10.
The intermediate layer 12 may be formed directly on the piston ring base material 11, or may be formed on the surface after the nitriding treatment, i.e., on the underlying layer 11a including the wear-resistant coating film. The intermediate layer 12 improves the adhesion between the piston ring base material 11 and the coating film 1. If necessary, another layer may be provided between the intermediate layer 12 and the cover film 1 for the purpose of improving the adhesion therebetween. For example, a film having the same or substantially the same composition as that of the coating film 1 described later may be formed as the hard carbon base film.
(coating film)
As shown in fig. 2 to 4, when bright field TEM images of the cross section of the coating film 1 are observed, 2 hard carbon layers (W, B) are provided, which are indicated by 2 colors of white and black. The black hard carbon layer B and the white hard carbon layer W are laminated together to form a repeating unit (represented by symbol x in fig. 2), and the repeating unit is laminated in the thickness direction Y to form the coating film 1 having a total thickness in the range of 1 μm to 50 μm. The term "opposed" means a relative relationship of color tones when a cross section is observed by a bright-field TEM image, and the layer that appears black is the "black hard carbon layer B" and the layer that appears white is the "white hard carbon layer W".
When the coating film 1 is applied to the piston ring 10, as shown in fig. 5, the coating film 1 is formed on at least an outer peripheral sliding surface 16 on which the piston ring 10 slides in contact with a cylinder liner (not shown). The surface may be formed on any other surface, for example, the upper surface, the lower surface, or the inner circumferential surface of the piston ring 10. The order of lamination of the black hard carbon layer B and the white hard carbon layer W is not particularly limited. In the example of fig. 2, the repeating units having the black hard carbon layer B formed thereon and the white hard carbon layer W formed thereon are laminated, but the repeating units having the white hard carbon layer W formed thereon and the black hard carbon layer B formed thereon may be laminated. The repeating unit may have any form shown in fig. 2, and the black hard carbon layer B and the white hard carbon layer W constituting the repeating unit may be formed so as to be adjacent to each other. From the viewpoint of initial suitability, the uppermost hard carbon layer is preferably formed of a black hard carbon layer B having low hardness.
The relatively black hard carbon layer B has a high density and sp as in the prior art2/sp3Small ratio, excellent strength, low density and sp of hard carbon layer with relative white color2/sp3Large ratio, low friction and excellent chipping resistance. However, the coating film 1 in the present invention has a hardness different from that of the conventional coating film, and the black hard carbon layer B and the white hard carbon layer W adjacent to each other have a white hard carbonThe hard carbon layer B has a higher hardness than the hard carbon layer W. That is, the black hard carbon layer B has a lower hardness sp than the adjacent white hard carbon layer W2/sp3Smaller and higher density. In contrast, the white hard carbon layer W has a higher hardness sp than the adjacent black hard carbon layer B2/sp3Larger ratio and lower density. As shown in the results of examples, the coating film 1 formed of the laminate of the repeating units of the black hard carbon layer B and the white hard carbon layer W can provide the sliding member 10 excellent in chipping resistance, wear resistance, and peeling resistance (adhesion) due to the lamination effect of the hard carbon layers B, W having different properties.
Sp of black hard carbon layer B2/sp3For example, as shown in example 2 described later, the thickness of the coating film 1 may be increased gradually from the base material 11 side to the surface position. It should be noted that sp2/sp3Ratio is will [ sp2/(sp2+sp3)]For more simplified expression, it is expressed by "sp" described later2/sp3The ratio was measured by the method described in the column of the description of "ratio".
The hardness of the black hard carbon layer B is preferably in the range of 700 to 1600HV, more preferably 750 to 1200 HV. The Vickers hardness of the white hard carbon layer W is higher than that of the adjacent black hard carbon layer B, and is preferably within a range of 1200 to 2200HV, and more preferably within a range of 1250 to 1900 HV.
About sp2/sp3Sp of the black hard carbon layer B2/sp3The ratio is preferably in the range of 0.05 to 0.75. Sp of the white hard carbon layer W2/sp3Sp of the specific black hard carbon layer B2/sp3The ratio is large and preferably in the range of 0.20 to 0.80. Due to sp2/sp3Carbon bond (sp) represented by diamond in small-sized black hard carbon layer B3Bonds) are relatively numerous, and have a high density and thus a high hardness, but in the present invention, the density is high but the hardness is low. On the other hand, due to sp2/sp3Carbon bond (sp) represented by graphite in large white hard carbon layer W2A key) is relatively large in number,the density is low and thus the hardness is low, but in the present invention, the density is high and the hardness is high. The reason for this is considered to be due to the film formation process described later. In this specification, sp is2/sp3Can be measured by Transmission Electron Microscopy (TEM) combined with Electron Energy Loss Spectroscopy (EELS). Here, "high", "low", "large" and "small" mean relative height and size between the black hard carbon layer B and the white hard carbon layer W.
Regarding the thickness ratio (T1/T2), the ratio (T1/T2) of the thickness T1 of the black hard carbon layer B to the thickness T2 of the white hard carbon layer W is preferably in the range of 1/10 to 1.5/1. Since the thickness ratio of the repeating units (T1/T2) is within the above range, the thickness ratio can be arbitrarily controlled so as to be constant or variable in the thickness direction Y of the cover film 1. The change in the thickness ratio may be gradually increased or decreased, and the thickness ratio at the start of film formation or at the end of film formation may be set to a thickness ratio different from that of other portions.
For example, when the ratio of the thicknesses of the black hard carbon layer B and the white hard carbon layer W (T1/T2) is the same or substantially the same in the thickness direction Y of the coating film 1, the low friction property and the chipping resistance in each repeating unit are the same, and therefore, even when the wear of the coating film 1 gradually progresses, the chipping resistance and the wear resistance can be exhibited in a stable and constant state. For example, when the ratio of the thicknesses of the black hard carbon layer B and the white hard carbon layer W (T1/T2) is gradually changed in the thickness direction Y of the coating film 1, the low friction property and the chipping resistance of the repeating unit at the initial stage of sliding, and the low friction property and the chipping resistance of the repeating unit at the initial stage and thereafter can be intentionally made to act, and therefore the chipping resistance and the wear resistance can be controlled when the wear of the coating film 1 gradually progresses.
The thickness T of the repeating unit is preferably in the range of 0.2 to 2 μm. The thickness T of each repeating unit may be arbitrarily controlled to be within the above range.
The black hard carbon layer B may have a somewhat network-like, scaly, dendritic, or lamellar three-dimensional growth form at the interface on the white hard carbon layer W side. In such a growth form, white hard carbon may be contained in the black hard carbon layer B. The triangular wave-like form of the black hard carbon layer B was observed to be V-shaped (a form gradually expanding from the position of the fan rib (fan axis)) or radial with respect to the film growth direction. As is clear from fig. 3, 4, and 7, the thicker the black hard carbon layer B, the more easily the mesh is generated, and the whole becomes a slightly whitish black layer.
As shown in fig. 3, 4 and 7, the white hard carbon layer W was visually recognized to have a fine streak shape, and similarly, the black hard carbon layer B was also visually recognized to have a fine streak shape. The clear reason why such streaks are visually recognized in the respective layers (white hard carbon layer W and black hard carbon layer B) alternately stacked is not clear at present, but it is considered that this is based on a continuous change in the distance from the target when the coating film 1 is formed by rotation as in the case of forming the coating film 1 on the sliding surface of the ring-shaped piston ring.
The coating film 1 is preferably formed to have a total thickness in the range of 1 μm to 50 μm. For example, the formation of the coating film 1 having a thickness in the above range in which the black hard carbon layer B and the white hard carbon layer W are laminated can be achieved by, for example: as a film formation temperature (substrate temperature) in the PVD method, a film formation at 200 ℃ or lower and a film formation at more than 200 ℃ are alternately performed. When the film is formed at 200 ℃ or lower, it becomes sp2/sp3A slightly larger white hard carbon layer W. On the other hand, when the film is formed at a temperature exceeding 200 ℃, it becomes sp2/sp3A small black hard carbon layer B. The cover film 1 can be formed into a film having a thickness in the above range by alternately laminating these films.
A part of the cover film 1 may have a raised shape (not shown) extending between at least 2 stacked layers. The raised shape is a portion that looks like a raised formation, and is a portion that looks like a particle and a balloon. The layered state in the case where the ridge shape is present is not similarly layered so as to be aligned in the thickness direction Y, but is easily expressed mainly in the upper half portion, and appears to be disordered, but does not greatly affect the properties such as wear resistance and chipping resistance. The mechanism of formation of the ridge shape is not yet clarified, and it is considered that large particles probably form a film as a starting point.
The black hard carbon layer B and the white hard carbon layer W constituting the coating film 1 contain almost no hydrogen based on the film formation conditions. If the hydrogen content is not to be shown, it may be 0.01 atomic% or more and less than 5 atomic%. The hydrogen content can be determined by hfs (hydrogen Forward scattering) analysis, the remainder consisting essentially of carbon only, and preferably not containing elements other than N, B, Si and other unavoidable impurities.
(film formation of coating film)
As the coating film 1, a PVD method such as an arc PVD method or a sputtering PVD method can be used. Among these, it is preferable to use a carbon target and form the film by arc ion plating in which hydrogen atoms are not contained in the film forming raw material. For example, when the coating film 1 is formed by arc ion plating, ON/OFF of a bias, control of a bias value, adjustment of an arc current, heating control of a substrate by a heater, forced cooling of a substrate introduced into a cooling device in a jig (holder) where the substrate is set, and the like can be used as film formation conditions. In particular, in the present invention, in order to form the coating film 1, a bias is applied to the black hard carbon layer B to form the coating film, and a bias in a range of 0V or less (for example, more than 0V to-50V or less) is applied to the white hard carbon layer W to form the coating film.
sp2/sp3The black hard carbon layer B having a ratio of 0.05 to 0.75 is formed under a bias causing a temperature rise. The bias voltage may be set to, for example, a range of-100 to-300V, the arc current at that time may be in a range of 40 to 120A, and the substrate temperature may be in a range of 100 to 300 ℃. On the other hand, sp2/sp3The white hard carbon layer (W) having a ratio of 0.20 to 0.80 is formed under a bias that does not cause a temperature rise. The bias voltage may be set to 0V or, for example, to a range of more than 0V to-50V, and the arc current at this time may be set to a range of 40 to 120A, so that the film formation is performed while gradually decreasing the substrate temperature without increasing the substrate temperature. The substrate temperature may be controlled by arc current or heater temperatureAnd the pressure in the furnace, etc. are adjusted by other means than the adjustment of the bias voltage. Further, the pressure in the furnace was set to 10-4～5×10-1In the case of a vacuum atmosphere of Pa, a hard carbon layer having low friction and high abrasion resistance can be obtained as compared with the case of introducing hydrogen gas or nitrogen gas, and therefore, this is preferable.
(sp2/sp3Than)
The hard carbon layer is a carbon bond sp represented by graphite2Bond and carbon bond sp represented by diamond3A membrane in which bonds are present in mixture. Here, 1s → π is determined by EELS analysis (Electron Energy-Loss Spectroscopy)＊Intensity sum 1s → σ＊Intensity, 1s → pi＊Intensity as sp2Intensity, 1s → σ＊Intensity as sp3Intensity, the ratio of which is 1s → π＊Intensity sum 1s → σ＊Ratio of intensities, [ sp ]2/(sp2+sp3)]Ratio (sometimes abbreviated as "sp2/sp3Ratio ". ). Thus, sp as described in the present invention2/sp3The ratio refers precisely to the pi/sigma intensity ratio. Specifically, a spectral imaging method in STEM (scanning TEM) mode was applied, and the sample absorption current was 10 at an acceleration voltage of 200kV-9A. EELS obtained at a 1nm pitch under the condition that the spot size diameter of the electron beam is 1nm are integrated, and sp is calculated by taking the C-K absorption spectrum as average information from about 10nm area2/sp3And (4) the ratio.
The bombardment treatment using a carbon target may be performed before the black hard carbon layer B is formed and before the white hard carbon film layer W is formed. The bombardment treatment may be performed before all of the hard carbon film layers B, W of black and white are formed, or may be performed only before the black hard carbon layer B is formed, or may be performed only before the white hard carbon layer W is formed. In the example shown in fig. 7, the carbon layer formed by the bombardment treatment was visually recognized only just under the black hard carbon layer B.
Examples
Hereinafter, the coating film and the sliding member of the present invention will be described in detail by referring to examples and reference examples.
[ example 1]
A piston ring is applied as the sliding member 10. When a composition comprising C: 0.65 mass%, Si: 0.38 mass%, Mn: 0.35 mass%, Cr: 13.5 mass%, Mo: 0.3 mass%, P: 0.02 mass%, S: 0.02 mass%, remainder: a40 μm nitrided layer was formed by nitriding treatment on a piston ring base material 11 (diameter: 88mm, ring radial width: 2.9mm, ring axial width: 1.2mm) of iron and inevitable impurities, and a metallic chromium layer having a thickness of 0.2 μm was formed as an intermediate layer 12 by ion plating. Next, a coating film 1 was obtained by forming a repeating unit of the black hard carbon layer B and the white hard carbon layer W on the intermediate layer 12 using an arc ion plating apparatus using a carbon target.
The black hard carbon layer B was formed to a thickness T1 of 0.14. mu.m by arc discharge at a bias of-150V and an arc current of 40A for 8 minutes. The white hard carbon layer W formed on the black hard carbon layer B was subjected to arc discharge (arc current 40A) at a bias of 0V for 22 minutes, and was formed to have a thickness T2 of 0.41 μm. The thickness T of the repeating unit was 0.55. mu.m, and the repeating unit was formed 20 times to obtain a coating film 1 having a total thickness of 11 μm.
[ evaluation ]
A bright field TEM image of the cross section of the coated film 1 after the film formation was taken. As shown in fig. 3 and 4, it was confirmed that the black hard carbon layer B indicated by black and the white hard carbon layer W indicated by white were alternately laminated in the thickness direction in the coating film 1. In addition, sp2/sp3The ratio is in the range of 0.25 to 0.75 for each part of the black hard carbon layer B and in the range of 0.4 to 0.80 for each part of the white hard carbon layer W.
[ Observation of structural form ]
The cross-sectional photograph of the clad film 1 was obtained by taking a bright field TEM image of the clad film 1 at an acceleration voltage of 200 kV. The total thickness of the coating film 1 and the thicknesses of the black hard carbon layer B and the white hard carbon layer W were determined from a bright field TEM image. For the measurement of the thickness, a piston ring having a coating film 1 formed in the vicinity of the center of the effective coating range of the arc ion plating apparatus used and a piston ring having coating films 1 formed in the vicinity of the upper end and the lower end were used as measurement samples. The ratio (T1/T2) of the thickness T1 of the black hard carbon layer B to the thickness T2 of the white hard carbon layer W was calculated.
[ abrasion resistance, chipping resistance, Low Friction Property, peeling resistance ]
The various properties of the coated film 1 after film formation were obtained by a friction and wear test method using an srv (schwingung reihunund und verschleiss) tester 120, which is generally performed in the evaluation of automobile sliding members. Specifically, as shown in fig. 6, in a state where the sliding surface of the frictional wear test sample 20 was in contact with the SUJ2 material as the sliding object 21, 5W-30 (no Mo-DTC) was used as a lubricating oil, and the sliding surface of the frictional wear test sample 20 was observed with a microscope while applying a load of 1000N and sliding back and forth for 10 minutes and 60 minutes under each load. In fig. 6, reference numeral 12 denotes an intermediate layer, and reference numeral 1 denotes a cover film.
It was confirmed that the obtained coating film 1 showed constant and stable chipping resistance and abrasion resistance without peeling or chipping, and was excellent in peeling resistance (adhesion).
The coating film 1 obtained in this experiment has good chipping resistance and wear resistance, and also has good aggressivity to the subject material (i.e., has little aggressivity to the subject material), and therefore has stable sliding characteristics to both the coating film 1 and the subject material. A sliding member such as a piston ring to which a high load is applied and a coating film are particularly desired to have such characteristics that the sliding member can be produced to have stable chipping resistance and wear resistance and excellent peeling resistance (adhesion) as compared with a sliding member not having such characteristics.
[ example 2]
In example 2, a piston ring was also used as the sliding member 10, the same piston ring base material 11 as in example 1 was used, and the nitrided layer and the intermediate layer 12 were also formed in the same manner as in example 1. The repeating units of the black hard carbon layer B and the white hard carbon layer W were also formed on the intermediate layer 12 by an arc ion plating apparatus using a carbon target in the same manner as in example 1, to obtain a coating film 1. In this example, when the black hard carbon layer B and the white hard carbon layer W were repeatedly formed, a carbon layer (see the thin white layer of FIG. 7) was formed by bombardment treatment (bias voltage: an arbitrary voltage of-500V to-2000V, specifically, -1000V) before the formation of the black hard carbon layer B.
As the film formation conditions in example 2, the black hard carbon layer B was subjected to arc discharge for 10 minutes under a bias of-150V and an arc current of 40A, and the black hard carbon layer B was formed to a thickness T1 of 0.18. mu.m. The white hard carbon layer W formed on the black hard carbon layer B was subjected to arc discharge (arc current 40A) at a bias of-30V for 20 minutes, and the white hard carbon layer W was formed to a thickness T2 of 0.35. mu.m. The thickness T of the repeating unit was 0.53. mu.m, and the repeating unit was formed 20 times to obtain a coating film 1 having a total thickness of 10.6. mu.m.
[ evaluation of example 2]
A bright field TEM image of a cross section of the coating film 1 of example 2 was taken and shown in fig. 7. As shown in fig. 7, it was confirmed that the black hard carbon layer B indicated by black and the white hard carbon layer W indicated by white were alternately laminated in the thickness direction in the coating film 1. As shown in fig. 7, fine streaks were observed in the white hard carbon layer W, and fine streaks were also observed in the black hard carbon layer B. Sp of the coating film 12/sp3The ratio is in the range of 0.05 to 0.55 for each part of the black hard carbon layer B and in the range of 0.20 to 0.70 for each part of the white hard carbon layer W. The hard carbon layer (B) has a Vickers hardness of 700-1100 HV, and the hard carbon layer (W) has a Vickers hardness of 1200-1900 HV higher than that of the adjacent hard carbon layer (B).
In the measurement of vickers hardness, since the thickness T (═ T1+ T2) of the repeating unit in example 2 was 0.53 μm, the thickness T1 of the black hard carbon layer B was 0.18 μm, and the thickness T2 of the white hard carbon layer W was 0.35 μm, which were thin, the measurement of the hardness of each of the individual layers of the black hard carbon layer B and the white hard carbon layer W in the cross section was almost impossible in the conventional measurement technique at the highest level. In addition, even when the measurement is performed from the surface, the thickness is small and the hardness of the lower layer is affected, which is difficult in the measurement technique of the highest level in the related art. Therefore, the vickers hardness here was evaluated by the results of measurement of the thickness of each of the black hard carbon layer B and the white hard carbon layer W.
Specifically, since the hardness is affected by the film formation temperature, in example 2, the substrate temperature at the end of the film formation of the black hard carbon layer B accompanied by a temperature increase is represented by TBThe substrate temperature at the end of the formation of the white hard carbon layer W with a temperature decrease is denoted as TWWhen, TB＞TW. In the case of forming a single layer of the black hard carbon layer B, the black hard carbon layer B is formed at 0.18 μm, and then the substrate temperature is cooled to as low as TWAt the time of arrival of TWAt that time, the black hard carbon layer B was formed to have a thickness of 0.18. mu.m. Then, the substrate temperature is lowered to T by repeatingWThe single-layer coating film obtained by forming only the black hard carbon layer B of example 2 was obtained by the cooling and the forming of the black hard carbon layer B. On the other hand, in the case of forming a single layer of the white hard carbon layer W, the white hard carbon layer W is formed to have a thickness of 0.35 μm, and then heated by a heater until the substrate temperature rises to TBUntil T is reachedBAt that time, the formation of the white hard carbon layer W was started and was 0.35 μm. Then, the temperature of the substrate is raised to T by repeatingBThe single-layer coating film obtained by forming only the white hard carbon layer W of example 2 was obtained by the heating and the formation of the white hard carbon layer W. In the measurement of the hardness from the surface, the single-layer coating films of the black hard carbon layer B and the white hard carbon layer W formed in a film thickness (6 μm or more) not affected by the substrate were adjusted to have a surface roughness ra0.05, and the vickers hardness was measured from the surface layer by a vickers hardness tester with a load of 100 gf. In this example, the measurement was carried out by the Vickers hardness measured in this wayEvaluation was carried out.
[ example 3]
In example 3, a piston ring was also used as the sliding member 10, the same piston ring base material 11 as in example 1 was used, and the nitrided layer and the intermediate layer 12 were also formed in the same manner as in example 1. The repeating units of the black hard carbon layer B and the white hard carbon layer W were also formed on the intermediate layer 12 by an arc ion plating apparatus using a carbon target in the same manner as in example 1, to obtain a coating film 1. In this example as well, a carbon layer was formed by bombardment treatment before forming the black hard carbon layer B, as in example 2.
As the film formation conditions in example 3, the black hard carbon layer B was subjected to arc discharge for 8 minutes under a bias of-130V and an arc current of 40A, and the black hard carbon layer B was formed to a thickness T1 of 0.13. mu.m. The white hard carbon layer W formed on the black hard carbon layer B was subjected to arc discharge (arc current 40A) at a bias of-50V for 22 minutes to form a white hard carbon layer W having a thickness T2 of 0.39. mu.m. The thickness T of the repeating unit was 0.52. mu.m, and the repeating unit was formed 20 times to obtain a coating film 1 having a total thickness of 10.4. mu.m.
[ evaluation of example 3]
The same applies to the clad film 1 of example 3, and a bright field TEM image of a cross section thereof shows the same form as that of fig. 7. Sp of the coating film 12/sp3The ratio is in the range of 0.05 to 0.35 for each part of the black hard carbon layer B and in the range of 0.20 to 0.50 for each part of the white hard carbon layer W. The hard carbon layer (B) has a Vickers hardness of 1050-1600 HV, and the hard carbon layer (W) has a Vickers hardness of 1650-2200 HV higher than that of the adjacent hard carbon layer (B). The vickers hardness of example 3 was also measured by the same method as in example 2.
The results of examples 1 to 3 were collated and sp was considered2/sp3The ratio is in the range of 0.05 to 0.75 for each part of the black hard carbon layer B, and in the range of 0.20 to 0.80 for each part of the white hard carbon layer W. For Vickers hardness, the black hard carbon layer B can be considered as 700E1600HV, and the Vickers hardness of the white hard carbon layer W is higher than that of the adjacent black hard carbon layer B, and is within the range of 1200-2200 HV.
The present invention has been described above based on the embodiments, but the present invention is not limited to the above embodiments. Various modifications may be made to the above-described embodiments within the same or equivalent scope as that of the present invention.

Claims (14)

1. A sliding member having a coating film on a sliding surface on a base material,
when a cross section of the coating film is observed by a bright field TEM image, repeating units comprising a black hard carbon layer relatively represented by black and a white hard carbon layer relatively represented by white are laminated in a thickness direction, and have a total thickness in a range of 1 μm to 50 μm,
in the adjacent black hard carbon layer and white hard carbon layer, the hardness of the white hard carbon layer is higher than that of the black hard carbon layer, and [ sp ] of the white hard carbon layer2/(sp2+sp3)]The ratio is larger than the black hard carbon layer.
2. The slide member according to claim 1,
the ratio (T1/T2) of the thickness T1 of the black hard carbon layer to the thickness T2 of the white hard carbon layer is 1/10-1.5/1.
3. The sliding member according to claim 1 or 2,
the thickness of the repeating unit is in the range of 0.2-2 μm.
4. The sliding member according to any one of claims 1 to 3,
the hard carbon layer has a Vickers hardness of 700-1600 HV, and the hard carbon layer has a Vickers hardness of 1200-2200 HV and is higher than the Vickers hardness of the adjacent hard carbon layers.
5. The sliding member according to any one of claims 1 to 4,
(sp) of the black hard carbon layer2/(sp2+sp3)]A ratio of [ sp ] of the white hard carbon layer is in the range of 0.05-0.752/(sp2+sp3)]A ratio of [ sp ] is in the range of 0.20 to 0.80 and is larger than the black hard carbon layer2/(sp2+sp3)]And (4) the ratio.
6. The sliding member according to any one of claims 1 to 5,
when a cross section is observed through a bright field TEM image, a hard carbon base film is arranged between the base material or a base film arranged on the base material and the coating film.
7. The sliding member according to any one of claims 1 to 6,
and when the section is observed through a bright field TEM image, a hard carbon surface film is arranged on the coating film.
8. The sliding member according to any one of claims 1 to 7,
(sp) of the black hard carbon layer2/(sp2+sp3)]The ratio gradually increases from the base material side to the surface position in the thickness direction of the cover film.
9. The sliding member according to any one of claims 1 to 8,
the white hard carbon layer has a fine streak shape.
10. The sliding member according to any one of claims 1 to 9,
the black hard carbon layer has a fine streak shape.
11. The sliding member according to any one of claims 1 to 10,
the black hard carbon layer and the white hard carbon layer have carbon layers formed by bombardment treatment directly below the respective layers.
12. The sliding member according to any one of claims 1 to 11,
the sliding member is a piston ring.
13. A method for manufacturing a sliding member having a coating film on a sliding surface on a base material,
when a cross section of the coating film is observed by a bright field TEM image, repeating units comprising a black hard carbon layer relatively represented by black and a white hard carbon layer relatively represented by white are laminated in a thickness direction, and have a total thickness in a range of 1 μm to 50 μm,
the black hard carbon layer is formed under a bias that causes a temperature increase, and the white hard carbon layer is formed under a bias that does not cause a temperature increase.
14. A coating film in which repeating units comprising a black hard carbon layer represented by black and a white hard carbon layer represented by white are laminated in the thickness direction when the cross section thereof is observed by a bright field TEM image, and which has a total thickness in the range of 1 to 50 [ mu ] m,
in the adjacent black hard carbon layer and the white hard carbon layer, the hardness ratio of the white hard carbon layer is higher than that of the black hard carbon layer and that of the white hard carbon layer2/(sp2+sp3)]The ratio is larger than the black hard carbon layer.
CN202080068880.XA 2019-09-30 2020-09-30 Sliding member, method for producing same, and coating film Pending CN114466950A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2019178891 2019-09-30
JP2019-178891 2019-09-30
PCT/JP2020/037281 WO2021066058A1 (en) 2019-09-30 2020-09-30 Sliding member and method for producing same, and coating film

Publications (1)

Publication Number Publication Date
CN114466950A true CN114466950A (en) 2022-05-10

Family

ID=75338109

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202080068880.XA Pending CN114466950A (en) 2019-09-30 2020-09-30 Sliding member, method for producing same, and coating film

Country Status (5)

Country Link
US (1) US11946010B2 (en)
EP (1) EP4039846A4 (en)
JP (1) JP7290171B2 (en)
CN (1) CN114466950A (en)
WO (1) WO2021066058A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021066058A1 (en) * 2019-09-30 2021-04-08 日本ピストンリング株式会社 Sliding member and method for producing same, and coating film
EP4281601B1 (en) * 2022-01-20 2024-01-03 Nanofilm Technologies International Limited Carbon coated electrodes
WO2024063157A1 (en) * 2022-09-22 2024-03-28 日本ピストンリング株式会社 Sliding member, method for manufacturing same, and coating film

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012063735A1 (en) * 2010-11-09 2012-05-18 株式会社ニコン Carbon thin film, mold for molding optical element and method for producing optical element
JP2015083875A (en) * 2014-11-25 2015-04-30 Ｔｐｒ株式会社 Piston ring
JP2017171988A (en) * 2016-03-23 2017-09-28 日本アイ・ティ・エフ株式会社 Coated film, method for manufacturing the same, and pvd apparatus
JP2018003880A (en) * 2016-06-28 2018-01-11 株式会社リケン Slide member
US20180371608A1 (en) * 2015-12-18 2018-12-27 Nippon Itf, Inc. Coating film, manufacturing method therefor, and pvd apparatus
JP6669922B1 (en) * 2019-06-12 2020-03-18 Ｔｐｒ株式会社 piston ring
US20200217416A1 (en) * 2017-06-20 2020-07-09 Nippon Piston Ring Co., Ltd. Sliding member and coating film
US20220396746A1 (en) * 2019-09-30 2022-12-15 Nippon Piston Ring Co., Ltd. Sliding member, manufacturing method thereof, and coating film

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012219930A1 (en) * 2012-10-31 2014-04-30 Federal-Mogul Burscheid Gmbh Sliding element, in particular piston ring, with a coating
CN104838183B (en) * 2012-12-11 2017-03-22 株式会社理研 Piston ring sprayed coating, piston ring, and method for producing piston ring sprayed coating
CN107075659B (en) * 2014-09-17 2020-07-28 日本Itf株式会社 Coating film and method for producing same
US10634249B2 (en) * 2015-08-10 2020-04-28 Nippon Itf, Inc. Piston ring and engine
JP6343266B2 (en) * 2015-09-09 2018-06-13 株式会社リケン Sliding member and piston ring
JP6413060B1 (en) * 2017-05-11 2018-10-31 日本アイ・ティ・エフ株式会社 Hard carbon film, method for producing the same, and sliding member
JP6511126B1 (en) * 2017-12-27 2019-05-15 株式会社リケン Sliding member and piston ring
BR112020025012B1 (en) * 2018-06-29 2022-02-08 Tpr Co., Ltd PISTON RING

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012063735A1 (en) * 2010-11-09 2012-05-18 株式会社ニコン Carbon thin film, mold for molding optical element and method for producing optical element
JP2015083875A (en) * 2014-11-25 2015-04-30 Ｔｐｒ株式会社 Piston ring
US20180371608A1 (en) * 2015-12-18 2018-12-27 Nippon Itf, Inc. Coating film, manufacturing method therefor, and pvd apparatus
JP2017171988A (en) * 2016-03-23 2017-09-28 日本アイ・ティ・エフ株式会社 Coated film, method for manufacturing the same, and pvd apparatus
JP2018003880A (en) * 2016-06-28 2018-01-11 株式会社リケン Slide member
US20200217416A1 (en) * 2017-06-20 2020-07-09 Nippon Piston Ring Co., Ltd. Sliding member and coating film
JP6669922B1 (en) * 2019-06-12 2020-03-18 Ｔｐｒ株式会社 piston ring
US20220396746A1 (en) * 2019-09-30 2022-12-15 Nippon Piston Ring Co., Ltd. Sliding member, manufacturing method thereof, and coating film

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
代海洋: "《类金刚石薄膜的制备、结构与性能研究》", 哈尔滨工业大学出版社有限公司, pages: 109 - 197 *

Also Published As

Publication number Publication date
US20220396746A1 (en) 2022-12-15
JPWO2021066058A1 (en) 2021-04-08
WO2021066058A1 (en) 2021-04-08
EP4039846A4 (en) 2023-10-25
EP4039846A1 (en) 2022-08-10
US11946010B2 (en) 2024-04-02
JP7290171B2 (en) 2023-06-13

Similar Documents

Publication Publication Date Title
CN110770362B (en) Sliding member and coating film
CN114466950A (en) Sliding member, method for producing same, and coating film
JP4251738B2 (en) Hard coating and covering member
CN102459688B (en) Protective coating, a coated member having a protective coating as well as method for producing a protective coating
CN108368602B (en) Coating film, method for producing same, PVD apparatus, and piston ring
JP6494505B2 (en) Hard carbon film
JP6472389B2 (en) Piston ring and manufacturing method thereof
JP2008286354A (en) Sliding member
JP6557342B2 (en) Piston ring and manufacturing method thereof
JP6718452B2 (en) Piston ring and manufacturing method thereof
JP5141654B2 (en) Sliding parts
US20240093344A1 (en) Hard carbon coatings with improved adhesion strength by means of hipims and method thereof
JP2006250348A (en) Sliding member
JP7451848B2 (en) Sliding member, its manufacturing method and coating film
JP2018076958A (en) piston ring
JP2019082241A (en) piston ring
WO2024063157A1 (en) Sliding member, method for manufacturing same, and coating film
CN114641588A (en) Substrate with a molybdenum nitride layer system and coating method for producing a layer system
JP2018172706A (en) Hard carbon coating film
WO2021140851A1 (en) Sliding member and piston ring

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination